Nothing Special   »   [go: up one dir, main page]

CN1238421C - Epoxy resin composition for packaging semiconductor and semiconductor device thereof - Google Patents

Epoxy resin composition for packaging semiconductor and semiconductor device thereof Download PDF

Info

Publication number
CN1238421C
CN1238421C CNB991251504A CN99125150A CN1238421C CN 1238421 C CN1238421 C CN 1238421C CN B991251504 A CNB991251504 A CN B991251504A CN 99125150 A CN99125150 A CN 99125150A CN 1238421 C CN1238421 C CN 1238421C
Authority
CN
China
Prior art keywords
epoxy resin
curing catalyst
composition
microcapsule
component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CNB991251504A
Other languages
Chinese (zh)
Other versions
CN1256288A (en
Inventor
池村和弘
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Denko Corp
Original Assignee
Nitto Denko Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Publication of CN1256288A publication Critical patent/CN1256288A/en
Application granted granted Critical
Publication of CN1238421C publication Critical patent/CN1238421C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/188—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using encapsulated compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/10—Details of semiconductor or other solid state devices to be connected
    • H01L2924/11—Device type
    • H01L2924/12—Passive devices, e.g. 2 terminal devices
    • H01L2924/1204—Optical Diode
    • H01L2924/12044—OLED
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12528—Semiconductor component

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Epoxy Resins (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

An epoxy resin composition for semiconductor encpsulation, which is excellent in both storage stability and rapid curability, is disclosed. The epoxy resin composition for semiconductor encapsultion comprises (A) an epoxy resin, (B) a phenolic resin, and a combination of (C) a cure accelerator and (D) cure accelerator-containing microcapsules having a core/shell structure in which a cure accelerator as a core is encapsulated in a thermoplastic resin shell.

Description

Epoxy resin composition for packaging semiconductor and semiconducter device
The present invention relates to have the epoxy resin composition for packaging semiconductor of excellent curing performance and storage stability and the semiconducter device that encapsulates with this composition epoxy resin.
Such as semiconductor element fields such as transistor, integrated circuit (IC) chip and large scale integrated chips, based on cost be suitable for the consideration of scale operation, present generally popular plastic encapsulation.The composition epoxy resin thing has been widely used as encapsulation and has used resin, and has obtained gratifying result.Particularly comprise Resins, epoxy, as the composition epoxy resin of lacquer resins (novolak phenolic resin), curing catalyst and the mineral filler (as silica powder) of stiffening agent since the encapsulation of its excellence often adopted by people.
In recent years, the competition of plastic encapsulation material price heats up.As the means that reduce cost, enhanced productivity for the shortening shaping cycle already and done all effort.The existing trend that increases of the demand of the packaged material that curing performance is improved to some extent, wherein the amount by increase curing catalyst to be added satisfies this demand.
Curing reaction takes place in the composition epoxy resin that adds curing catalyst in advance when storage.When adding a large amount of curing catalyst, said composition can react rapidly before use especially, the extremely short and working efficiency reduction working life that has.Therefore recently proposed to use the composition epoxy resin that contains the curing catalyst microcapsule.
Though have excellent storage stability, but containing as single curing promotes the composition epoxy resin of curing catalyst of the encapsulation of component that following shortcoming is arranged: owing to fusion of microcapsule housing and destruction need be answered role so postponed curing catalyst in the resin composition for sealing semiconductor moulding.Consequently, such composition is difficult to rapid curing.This defective is outstanding especially when mold temperature low (general 140-180 ℃).
Based on above-mentioned all situations, one of purpose of the present invention provides a kind of composition epoxy resin of semiconductor-sealing-purpose, and said composition had both had excellent storage stability, has excellent rapid solidified nature again.
Another object of the present invention provides a kind of semiconducter device that uses composition epoxy resin.
To achieve these goals, provide a kind of composition epoxy resin of semiconductor-sealing-purpose in first embodiment of the present invention, contained:
(A) Resins, epoxy;
(B) resol (phenol resin);
(C) curing catalyst; With
(D) contain the microcapsule of curing catalyst, have core/shell structure, wherein the curing catalyst as the nuclear core is packaged in the housing that contains thermoplastic resin.
The semiconducter device that contains with the semiconductor element of above-mentioned composition epoxy resin encapsulation is provided in second embodiment of the present invention.
In order to solve the variety of problems that usual composition epoxy resin brought of semiconductor-sealing-purpose, the inventor has carried out a series of research.In order to satisfy conflicting storage stability and the requirement of solidified nature rapidly, the inventor focuses on research on the batch mixing additive.Discover curing catalyst and packed curing catalyst (microcapsule that promptly contain curing catalyst), combine use and can obtain a kind of packaged material that satisfies above-mentioned two requirements, thereby realize the present invention.
In a preferred embodiment of the invention, curing catalyst is determined with the blending ratio that contains the microcapsule of curing catalyst, all improves to some extent to guarantee rapid solidified nature and storage stability.
In another preferred embodiment, the microcapsule housing that contains curing catalyst contains the polyureas for preparing by specific ratio of mixture with specific triisocyanate compound.Because the fail temperature of housing can suitably be controlled, so can be with other component melt kneading under the high temperature about 130 ℃ according to these microcapsule of this scheme.This has reduced with regard to the viscosity that means this kneading system, and its advantage is fully to mediate, and the composition epoxy resin that obtains having the homodisperse component.
In another preferred embodiment of the present invention, make Resins, epoxy with biphenyl type epoxy resin, the flowability of such composition epoxy resin increases, and has promptly improved processability.
In another preferred embodiment, make resol with phenol aralkyl resin.At this moment, the flowability of composition epoxy resin improves, and the solidifying product of anti-welding that water absorbability and Young's modulus decrease etc. is provided.
To introduce the present invention in detail below.
Epoxy resin composition for semiconductor encapsulation according to the present invention is by (A) Resins, epoxy, (B) resol, (C) curing catalyst; (D) contain the microcapsule preparation of specific curing catalyst.Composition epoxy resin of the present invention generally provides with powder or powder film-making agent form.
Resins, epoxy as component (A) is not particularly limited, and it comprises general various types of Resins, epoxy as the semiconductor-sealing-purpose resin, for example bisphenol-A type Resins, epoxy, by various phenol synthetic novolac epoxy resins.This based epoxy resin both can use separately also can mix use with two or more.Be the Resins, epoxy that solid, fusing point surpass room temperature under the preferred room temperature in these Resins, epoxy.Suitable Resins, epoxy has biphenyl type epoxy resin and novolac epoxy resin.In the novolac epoxy resin, epoxy equivalent (weight) is 160-250, softening temperature 50-130 ℃ suit.The Resins, epoxy of formula that biphenyl type epoxy resin comprises following (IV) representative:
Figure C9912515000051
Wherein: R 1, R 2, R 3And R 4Can be identical or different group, respectively is hydrogen atom or the alkyl with 1-4 carbon atom.
(IV) in the formula, alkyl comprises the straight or branched low alkyl group, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl and the tertiary butyl.From agent of low hygroscopicity and reactive consideration, preferably use wherein R 1, R 2, R 3And R 4Be the biphenyl type epoxy resin of methyl and R wherein 1, R 2, R 3And R 4Be the mixture of the biphenyl type epoxy resin of hydrogen atom by 1: 1 ratio (weight) composition.
Resol as the component (B) of epoxy resin hardener comprises lacquer resins, for example phenol lacquer resins, cresols lacquer resins, tert-butyl phenol lacquer resins and nonyl phenol lacquer resins; Cresols type resol; Phenol aralkyl resin; And polycarboxylated styrene, for example poly--para hydroxybenzene ethene.These resins both can use separately also and wherein two or more can have been mixed use.Preferred lacquer resins and phenol aralkyl resin wherein.In the lacquer resins, preferred softening temperature 50-110 ℃, hydroxyl equivalent are the resin of 100-150.Phenol aralkyl resin comprises those resins of formula V representative:
Figure C9912515000052
Wherein, n is 0 or positive integer.
In above-mentioned formula V, the positive integer of n preferred 0 or 1-40, more preferably 0 or the positive integer of 1-30.In the phenol aralkyl resin of formula V representative, preferred hydroxyl equivalent be 150-220, particularly hydroxyl equivalent be 150-200, softening temperature 40-110 ℃, particularly softening temperature is 50-90 ℃ an aralkyl resin.
For the Resins, epoxy as component (A) of every epoxy equivalent (weight), be that the hydroxyl equivalent of resol is 0.5-2.0 as the resol preferable amount of component (B), preferred 0.8-1.2.As surpassing this preferable range, said composition often can not fully be hardened, resulting cured resin degradation.
Curing catalyst as component (C) does not have special requirement.Any known curing catalyst that is used for Resins, epoxy can use, for example tertiary amine compounds, imidazolium compounds, quaternary ammonium salt, organic metal salt, phosphorus compound (for example triphenylphosphine and tetraphenyl boric acid tetraphenylphosphonium), phenodiazine two heterocyclic alkenes (for example 1,8-phenodiazine two heterocycles [5,4,0] undecane alkene-7), the derivative of these compounds all can use.These promotor both can add separately also can mix use with two or more.Preferred phosphorus compound and 1 in these curing catalysts, 8-phenodiazine two heterocycles [5,4,0] undecane alkene-7.
The microcapsule that contain curing catalyst as component (D) have core/shell structure, and the nuclear core that contains curing catalyst is packaged in the shell that contains the attached fat of thermoplasticity.
The known curing catalyst that is used to examine core does not have strict demand.Consider the processibility of little encapsulation or the characteristic of gained microcapsule, suitable under the room temperature being liquid curing catalyst.Term " under the room temperature for liquid " is though to mean this promotor at room temperature itself be exactly liquid or at room temperature be solid-state but promptly be liquefied in being dissolved in or being scattered in suitable organic solvent.
Curing catalyst to be packaged comprises amine, imidazoles, phosphorus compound, boron compound and phosphorus-boron compound.The example of the suitable curing catalyst that can enumerate has the replacement guanidine, for example ethyl guanidine, trimethylammonium guanidine, guanidines and diphenylguanidine; 3-(replace or unsubstituted phenyl)-1,1-dimethyl urea, 3-(3, the 4-dichlorophenyl)-1 for example, 1-dimethyl urea, 3-phenyl-1,1-dimethyl urea and 3-(4-chloro-phenyl-)-1,1-dimethyl urea; Imidazolidine derivatives, for example glyoxal ethyline quinoline, 2-benzylimidazoline, 2-undecyl imidazole quinoline and 2-heptadecyl tetrahydroglyoxaline; One aminopyridine, for example 2-aminopyridine; Aminimide, N for example, N-dimethyl-N-(2-hydroxyl-3-allyloxy propyl group) amine-N '-lactic amide; Organo phosphorous compounds, for example ethyl phosphine, propyl group phosphine, butyl phosphine, Phenylphosphine, trimethyl-phosphine, triethyl phosphine, tributylphosphine, tri octyl phosphine, triphenylphosphine, tricyclohexyl phosphine, triphenylphosphine/triphenyl borane title complex and tetraphenyl boric acid tetraphenylphosphonium; With the diazabicylo alkene, for example 1,8-diazabicylo [5,4,0] undecylene-7 and 1,5-diazabicylo [4,3,0] nonene-5.These curing catalysts both can use separately also can mix use with its two or more.For the situation of encapsulation and processing, preferred organo phosphorous compounds.
Can add any in the described housing at room temperature for liquid organic solvent, unless this dissolution with solvents housing.Suitable organic solvent comprises ethyl acetate, methylethylketone, acetone, methylene dichloride, dimethylbenzene, toluene, tetrahydrofuran (THF) and so-called oils compound, for example phenyl xylyl ethane and dialkyl group naphthalene.
Various thermoplastic resins all can be used as the shell material, do not have restriction especially.Preferred especially polyureas.Suitable polyureas comprises the polyureas by the triisocyanate preparation of the triisocyanate of following formula (I) representative and formula (II) representative:
Figure C9912515000071
The compound of formula (I) representative (being called compound (I) down) can easily for example carry out addition reaction with 1 mole of trimethylol propane and 3 mole of two isocyanic acid dimethyl phenyl ester and obtain in ethyl acetate.
The compound of formula (II) representative (being called compound (II) down) can for example be used 1 mole of trimethylol propane and 3 mole 2 easily, and 4-toluene subunit vulcabond carries out addition reaction and can obtain in ethyl acetate.This reaction can be carried out in the presence of a small amount of polyurethane-reinforcement tin type catalyzer.
The general compound (II) that uses following formula (IIa) representative:
Figure C9912515000072
The mol ratio (I)/(II) of compound (I) and compound (II) is preferred 100/0 to 30/70, more preferably 70/30-50/50.If the mol ratio of compound (I) was lower than for 30 (mol ratio of compound (II) is higher than 70), the initial fail temperature of housing is up to 165 ℃, even higher, and the curability of composition epoxy resin has the trend of reduction when sealing on semiconductor element.As mol ratio is fixed in the preferable range, the fail temperature of housing will drop in 150 ℃ ± 15 ℃ such one desirable scopes.Especially in (I)/(II) mol ratio during in 70/30 to 50/50 scope, the fail temperature of housing will drop in 150 ℃ of-160 ℃ of scopes.This will make the mixing of component (A)-(D) under about 130 ℃ of pyritous molten states become easy.This will be difficult for the preparation of the usual composition epoxy resin that comprises the microcapsule that contain curing catalyst.Reduced like this and mediated the viscosity and the shearing force of system, and can fully mediate.The gained composition epoxy resin has homodisperse above-mentioned component thus, particularly has generally as auxiliary agent to be added on wherein mineral filler (hereinafter will introduce).
Preferred situation is, by the polyureas (hereinafter being called polyureas A) of compound (I) and the preparation of mixture (II)
The repeating unit that mainly comprises formula (III) representative:
Figure C9912515000081
Wherein: R represents divalent organic group; R 1And R 2Can be identical or different, be hydrogen atom or any monovalent organic radical group independently, wherein preferred hydrogen atom.
The polyureas A that mainly comprises the repeating unit of (III) formula representative is as allowing triisocyanate compound (I) and mixture (II) and water prepared in reaction.Compound (I) and mixture hydrolysis (II) obtain amine compound, and this product and the reaction of unreacted isocyanate groups (so-called from polyaddition) form polyureas A.
Polyureas A also can carry out polyaddition reaction by compound (I) and mixture (II) and polyamines and make.Any polyamines with two or more amino groups all can use.Diethyl triamine, triethyl tetramine, tetraethylenepentamine, 1,6-hexamethylene-diamine, 1,8-eight first subunit diamines, 1,12-ten dimethylene diamines, ortho-phenylene diamine ,-phenylenediamine, p-phenylenediamine, ortho-xylene base diamines ,-xylyl diamines, right-the xylyl diamines, menthanediamine, two (4-amino-3-methylcyclohexyl) methane, isophorone diamine, 1,3-diamino-cyclohexane and spiral shell-acetal diamines then is the example of the polyamines that suits.These polyamines both can use also separately two or more had been combined use.For the isolation or protective capability of formed housing, preferred diethyl triamine, triethyl tetramine and tetraethylenepentamine wherein.
The method of available any known formation microcapsule prepares the microcapsule that contain curing catalyst as component (D).The preferred interfaces polymerization forms the controlled housing of quality uniform thickness.
Realize preparing the interfacial polymerization of the microcapsule that contain curing catalyst as follows.Liquid as the curing catalyst itself that uses, then compound (I) and mixture (II) are dissolved in this curing catalyst, the oily solution that obtains is scattered in aqueous phase prepares the O/w emulsion.For the stability of this emulsion between polymerization period, dispersive oil droplet granularity is about the 0.05-50 micron, about preferred 0.05-20 micron.
If used is the solid curing catalyst that is dissolved in the organic solvent, then obtain S/O/W (solid phase/oil phase/water) emulsion.When oleophylic curing catalyst situation is exactly like this.On the other hand, be hydrophilic as solid promoter, then be difficult to prepare S/O/W type emulsion.At this moment, then can carry out interfacial polymerization and prepare O/O or S/O/O emulsion by the adjusting of solubleness.
The aqueous phase that polyamines or polyvalent alcohol are added to emulsion then causes addition polymerization and forms polyureas A housing at polyamines or polyvalent alcohol and the interface that is dissolved between the mixing isocyanate compound of oil phase, wherein is mixed with the curing catalyst as the nuclear core.
So the microcapsule that contain curing catalyst as component (D) of preparation can be separated it with currently known methods, and drying or spraying drying are given in for example centrifugation thereafter again.Component (D) dissolves in as in the Resins, epoxy of component (A) or in the resol as component (B).If needed, availablely organic solvent in the microcapsule is removed as methods such as vacuum-dryings.
The shearing force that when considering the blending epoxy composition microcapsule is applied, for microcapsule stability and dispersed for, preferred average particle size is the microcapsule of 0.05-20 micron, more preferably the 0.1-4 micron.Preferred microcapsule are spherical, also can be elliposoidal.As microcapsule is elliposoidal, flat and so on non-sphere, and promptly irregular as granular size, the arithmetic mean value of then using this particulate width and length is as mean particle size.
The preferred proportion of the curing catalyst of the encapsulation in the component (D) is 5-70% (a weight meter), more preferably 10-50% (weight meter).As be lower than 5% (weight meter), then have its reactive can hanging down and solidify the trend that needs the long time to causing.As surpassing 70% (weight meter),, cause being difficult to from other component, isolating curing catalyst just housing can be thinned to the insufficient strength that causes microcapsule.
Thickness of shell is with the preferred 3-25% of ratio of microcapsule granularity, more preferably 5-25%.So value is lower than 3%, and the physical strength of microcapsule is then not enough, thereby causes bearing the shearing force that applies when preparing composition epoxy resin.Than greater than 25%, will make the release of promotor not enough as thickness.
As the curing catalyst of component (C) and the preferred 95/5-1/99 of ratio of mixture, more preferably 20/80-3/97 (weight meter) as the microcapsule that contain curing catalyst of component (D).As (C)/(D) ratio of mixture in this preferable range, just then storage stability and rapidly solidified nature can further improve.
In per 100 parts component (A) and the gross weight (B), the preferred 0.5-6 weight part of component (C) and total amount (D) (hereinafter being called part), more preferably 1.0-4.5 part.Be lower than 0.5 part as (C) and total amount (D), the solidified nature of composition epoxy resin has the tendency of serious reduction during packaging semiconductor, at this moment can only provide unsafty semiconducter device.As above 6 parts, the curing of said composition is so rapid when the semiconductor packages moulding, cause said composition viscosity before covering semiconductor element fully just to increase, usually make the semiconducter device that obtains not fill (non-filling), wiring sweeps (wire sweep) or die-cushion plate distortion (diepad deformation).
Component (C) and the suitable combination of (D) forming comprise from triphenylphosphine, tetraphenyl boric acid four benzene phosphorus and 1,8-diazabicylo [5,4,0] mixture formed of the component (C) selected of undecylene-7 and the component (D) from triphenylphosphine and tetraphenyl boric acid four benzene phosphorus, selected.
The composition epoxy resin that comprises component (A)-component (D) also can comprise the mineral filler component (E) that adapts with purposes.Suitable mineral filler as component (E) comprises silicon oxide, clay, gypsum, lime carbonate, barium sulfate, aluminum oxide, beryllium oxide, silicon carbide and silicon nitride.Silicon oxide, particularly fused silica are most preferred mineral fillers.The preferred average particle size of mineral filler is the 0.1-80 micron.Gross weight in the Resins, epoxy component is a benchmark, and the preferable amount of mineral filler is 70-95%, more preferably 80-95%.
If necessary, except that component (A)-(E), composition epoxy resin of the present invention also can comprise other additive, for example fire retardant and Wax.The example of suitable fire retardant has line style phenolic aldehyde brominated epoxy resin, brominated bisphenol A Resins, epoxy, ANTIMONY TRIOXIDE SB 203 99.8 PCT, antimony pentaoxide and composition thereof.The example of suitable Wax has: higher fatty acid, high-grade aliphatic ester, higher fatty acid calcium salt and composition thereof.
For reducing stress, also can add silicone oil, silicon rubber, synthetic rubber etc. in the composition epoxy resin of the present invention, or, wherein also can add hydrotalcite and bismuth hydroxide plasma scavenging agent in order in moistureproof reliability test, to improve reliability.
Composition epoxy resin of the present invention can prepare with for example following method.Utilize earlier the microcapsule that contain curing catalyst of interfacial polymerization preparation as stated above as component (D).Immediately necessary component (A)-(D), selectivity component (E) and other essential additive are mixed together then, and are mediating as in the mixing roller one class kneader.Mixture melt kneading or in kneader etc., mediate in hot-rolling.After the cooling, mixture is pulverized.If necessary, again with institute's powder process tablet forming.
With known forming technique (typically being the low-pressure transfer die-casting technique) with composition epoxy resin packaging semiconductor of the present invention.
With with curing catalyst with the microcapsule that contain curing catalyst combine use as feature according to composition epoxy resin of the present invention, not only aspect storage stability, be better than the usual composition epoxy resin that only contains the curing catalyst of micro encapsulation not and also with the usual composition epoxy resin ratio that only contains the micro encapsulation curing catalyst, its curing speed is rapid.Semiconducter device with composition epoxy resin encapsulation of the present invention just has excellent reliability like this.
To further describe in detail the present invention below, but the present invention never only limits to the technical scheme introduced among these embodiment with embodiment and Comparative Examples.Unless otherwise indicated, all percentage number averages are by weight.
Prepare the microcapsule of using in each embodiment and each Comparative Examples that contain curing catalyst (D1-D5 microcapsule) as follows.
Microcapsule D1:
10.5 parts of compounds (I), 6.6 parts of compounds (IIa), 6.7 parts of triphenylphosphines (curing catalyst) and 4.8 parts of ethyl acetate are mixed with even oil phase.Compound (I) and compound (IIa) mol ratio are 6/4.By homogeneous mixer (8000 revolutions per seconds) this oil phase is emulsifiable in by 95 parts of distilled water and 5 parts of aqueous phases that polyvinyl alcohol is formed.This O/W emulsion is loaded in the polymerizer of band return line, agitator, dropping funnel.
The aqueous solution (13 parts) for preparing triethylenetetramine (3 parts) separately.With dropping funnel this water drop is added in the above-mentioned emulsion.Allow this system hour obtain the microcapsule D1 that forms by polyureas shell and triphenylphosphine nuclear core at 70 ℃ of following polyase 13s.The mean particle size of microcapsule D1 is 2 microns, is benchmark in the granularity, and its housing thickness rate is 20%.The fail temperature of housing is 150 ℃.
Microcapsule D2
Same quadrat method with above-mentioned preparation microcapsule D1 prepares microcapsule D2 (2 microns of mean particle sizes), but needs to change the mol ratio of compound (I)/compound (IIa) into 7/3.This capsular fail temperature is 140 ℃.
Microcapsule D3
Same quadrat method with above-mentioned preparation microcapsule D1 prepares microcapsule D3 (2 microns of mean particle sizes), but needs to change the mol ratio of compound (I)/compound (IIa) into 10/0.This capsular fail temperature is 110 ℃.
Microcapsule D4
Same quadrat method with above-mentioned preparation microcapsule D1 prepares microcapsule D4 (2 microns of mean particle sizes), but needs to change the mol ratio of compound (I)/compound (IIa) into 5/5.This capsular fail temperature is 155 ℃.
Microcapsule D5
Same quadrat method with above-mentioned preparation microcapsule D1 prepares microcapsule D5 (2 microns of mean particle sizes), but needs to change the mol ratio of compound (I)/compound (II) into 3/7.This capsular fail temperature is 165 ℃.
Other mixed composition that is used for each embodiment and Comparative Examples is as follows:
Resins, epoxy A1:
4,4 '-two (2, the 3-glycidoxy)-3,3 ', 5,5 '-tetramethyl-phenylbenzene (epoxy equivalent (weight): 200)
Resins, epoxy A2:
Cresols novolac epoxy resin (epoxy equivalent (weight): 198)
Bakelite B 1:
The phenol aralkyl resin of formula V representative, wherein n is 0-21, (hydroxyl equivalent: 175)
Bakelite B 2:
Phenol lacquer resins (hydroxyl equivalent: 105)
Curing catalyst C1:
Triphenylphosphine
Curing catalyst C2:
Tetraphenyl boric acid four benzene phosphorus
Curing catalyst C3:
1,8-diazabicylo [5,4,0] undecylene-7
Mineral filler: fused silica (mean particle size: 15 microns) through grinding
The Resins, epoxy of bromination:
Epoxy equivalent (weight): 275; Bromine amount: 36%
Embodiment 1-14 and Comparative Examples 1-4
Mix the material listed among the following table 1-3 and melt kneading in mixing roller.After the cooling, be ground into powder and obtain epoxy resin composition for semiconductor encapsulation.
Table 1
Embodiment number
1 2 3 4 5 6 7
Resins, epoxy (A) A1 - 85 85 85 85 85 85
A2 85 - - - - - -
Resol (B) B1 - 87 87 87 87 87 87
B2 52 - - - - - -
Curing catalyst (C) C1 - - - - - - -
C2 - - - - - - -
C3 1.4 2.5 2.5 2.5 2.5 2.5 0.2
The microcapsule (D) that contain curing catalyst D1 6/4* - 10 - - - - -
D2 7/3* 5.4 - 10 - - - 16.7
D3 10/0 * - - - 10 - - -
D4 5/5* - - - - 10 - -
D5 3/7* - - - - - 10 -
Mineral filler 1460 1620 1620 1620 1620 1620 1620
Polyethylene wax 3 3 3 3 3 3 3
The Resins, epoxy of bromination 20 20 20 20 20 20 20
ANTIMONY TRIOXIDE SB 203 99.8 PCT 20 20 20 20 20 20 20
(C)/(D) weight ratio 20/80 20/80 20/80 20/80 20/80 20/80 1/99
* (I)/(IIa) mol ratio
Table 2
Embodiment number
8 9 10 11 12 13 14
Resins, epoxy (A) A1 85 85 85 85 85 85 85
A2 - - - - - - -
Resol (B) B1 87 87 87 87 87 87 87
B2 - - - - - - -
Curing catalyst (C) C1 - - - 2.6 - - -
C2 - - - - 4.4 - -
C3 1.3 3.1 4.0 - - 4.9 4.2
The microcapsule (D) that contain curing catalyst D1 6/4* - - - - - - -
D2 7/3* 13 7.2 4.0 2.6 4.4 0.3 1.0
D3 10/0 * - - - - - - -
D4 5/5* - - - - - - -
D5 3/7* - - - - - - -
Mineral filler 1620 1620 1620 1620 1620 1620 1620
Polyethylene wax 3 3 3 3 3 3 3
The Resins, epoxy of bromination 20 20 20 20 20 20 20
ANTIMONY TRIOXIDE SB 203 99.8 PCT 20 20 20 20 20 20 20
(C)/(D) weight ratio 10/90 30/70 embodiment number 50/50 50/50 50/50 8 95/5 9 80/20 10
* (I)/(IIa) mol ratio
Table 3
Comparative example number
1 2 3 4
Resins, epoxy (A) A1 85 85 85 85
A2 - - - -
Resol (B) B1 87 87 87 87
B2 - - - -
Curing catalyst (C) C1 3.9 - - -
C2 - - - -
C3 - 5.2 - -
The microcapsule (D) that contain curing catalyst D1 6/4* - - 11 15
D2 7/3* - - - -
D3 10/0* - - - -
D4 5/5* - - - -
D5 3/7* - - - -
Mineral filler 1620 1620 1620 1620
Polyethylene wax 3 3 3 3
The Resins, epoxy of bromination 20 20 20 20
ANTIMONY TRIOXIDE SB 203 99.8 PCT 20 20 20 20
(C)/(D) weight ratio 100/0 100/0 0/100 0/100
* (I)/(IIa) mol ratio
Estimate the composition epoxy resin of each embodiment and each Comparative Examples system as follows.The results are shown in table 4 and the table 5.
1) 175 ℃ of following gelation times
With the fixed 175 ℃ of following gelation times of hot bench teat test.
2) solidify back hardness (175 ℃ * 50 seconds)
With this composition epoxy resin 175 ℃ of compacted unders 50 seconds.With the hardness under the hot state of Xiao Er D hardness tester mensuration cured resin.
3) storage stability
Close and be preheating to 175 ℃ ± 5 ℃ spiral flow moving molds and impose mold pressure.When mold pressure reaches 210 ± 10 kg/cm, powdered epoxy composition is added transmission material nest, use transfer plunger die casting.When transmit force reaches 70 ± 5 kg/cm, under this pressure, kept 1 minute and 50 seconds.After transfer plunger pressure release, eliminate mold pressure and open mould.Press the helical length after EMMI 1-66 standard test is shaped, be accurate to 2.5mm, obtain helical degree of mobilization value (SF value), this value is initial SF value.
It is 24.5mm that same powdered epoxy composition is made diameter, and thickness is the tablet of 20mm, and institute's film-making was placed 3 days down at 30 ℃.By above-mentioned same manner sheet is tested and to be obtained storing back SF value.Press following formula and calculate helical degree of mobilization retention rate with initial and storage back helical degree of mobilization:
Helical degree of mobilization retention rate (%)=(storage back SF value)/(initial SF value) * 100
4) formability and reliability
It is 24.5mm that powdered epoxy composition is made diameter, and thickness is the tablet of 20mm, and institute's film-making was placed 3 days down at 30 ℃.Following at 175 ℃ with this sheet die casting semiconducter device that have following characteristic with acquisition 90 seconds on semiconductor element:
80 pin quadruple flat package (80-Pin quadruple flat package, QFP-80): 14mm * 8mm * 2.7mm (t)
Lead frame (Lead frame): MF202
Semiconductor element: 8mm * 8mm * 0.37mm (thickness)
In 120 semiconducter device that make, write down the number of the semiconducter device of moulding fault.That is the semi-conductor package (QFP-80 that is undertaken by 10 injection volumes with shaping equipment (VPS-40, TOWA system); 14mm * 20mm * 2.7mm) also checks no filler and the empty situation of removing that exists.Find the space bore dia through the soft X-ray device is 0.1mm or discarded greater than the semiconducter device of this value.It is that 2 normal atmosphere, temperature are that 121 ℃, relative humidity are 100% pressure cooker (pressure cooker testing, hereinafter referred PCT) that the semiconducter device that will be used for testing is put in pressure.To the semiconducter device energising of this test, the semiconducter device of discarded short circuit.Scrap rate reaches 50% test period when measuring pressure cooker testing.
Table 4
Embodiment number The composition characteristic Processability PCT reliability (time of 50% scrap rate)
175 ℃ of gel times Xiao Er hardness D (175 ℃ * 50 seconds) Storage stability (%) Do not fill the scrap rate (%) that causes The space forms the scrap rate (%) that causes
1 17 75 88 0 2 260
2 20 73 81 0 4 320
3 21 73 82 0 6 290
4 18 76 78 0 4 300
5 25 72 82 0 4 330
6 27 71 84 0 3 310
7 30 70 97 0 3 280
8 27 71 92 0 4 290
9 24 74 84 0 6 310
10 21 75 81 0 3 330
11 22 77 80 0 6 300
12 23 76 82 0 5 360
13 15 81 70 0 2 240
14 17 80 71 0 2 250
Table 5
Embodiment The composition characteristic Processability PCT reliability (time of 50% scrap rate)
175 ℃ of gel times Xiao Er hardness D (175 ℃ * 50 seconds) Storage stability (%) Do not fill the scrap rate (%) that causes The space forms the scrap rate (%) that causes
1 16 75 66 17 388 60
2 14 83 52 27 322 70
3 40 61 99 0 13 160
4 33 66 99 0 9 170
Shown in the listed result of table 4, all compositions that make among the embodiment 1-14 all have high hardness (Xiao Er D) and high helical degree of mobilization retention rate, and this proof solidified nature and storage stability are all excellent.The moulding evidence does not have unfilled situation and space incidence extremely low.And, show that through the PCT test its moisture resistance is also satisfactory.These results clearly show that composition epoxy resin according to the present invention has high storage stability and excellent rapidly-curable, the therefore suitable high-reliability material of making packaging semiconductor.
In contrast, Comparative Examples 1 and 2 composition have low helical degree of mobilization retention rate, and this shows that its storage stability is poor.Therefore observe the generation of not filling and often having the space to exist, the result of PCT test is also poor.Though the composition of Comparative Examples 3 and 4 has excellent helical degree of mobilization retention rate, solidified nature is low and the result PCT test is also poor when short curing molding.
Contain Resins, epoxy (A), resol (C) and no matter rapid solidified nature and storage stability aspect all are excellent by the composition epoxy resin of the present invention that promotes solidified curing catalyst (C) and contain the mixture that (D) of the microcapsule of curing catalyst form.In the embodiment of excellence, component (C) and mixing specific energy (D) guarantee that further solidified nature and storage stability all can further improve.
In another preferred embodiment, the housing that contains the microcapsule of curing catalyst comprises with the polyureas of specific triisocyanate compound by specific ratio of mixture preparation.According to this preferred embodiment, can under about 130 ℃ high temperature, little glue be assisted with other component melt kneading together.This just means that the kneading system has the viscosity of reduction, and its advantage is can fully mediate to obtain a finely dispersed composition epoxy resin of each component.
In preferred embodiments, on the whole, make component (A) to guarantee mobile raising, promptly improve processability with xenyl Resins, epoxy.Also can further produce such effect with phenol aralkyl resin, promptly the water absorbability of the solidifying product of said composition and Young's modulus all will reduce, and this helps soldering resistance etc.
So the most suitable packaged material of making semiconductor element of composition epoxy resin according to the present invention.In addition, said composition also is applicable to other field, for example tackiness agent and paint field.

Claims (7)

1. the composition epoxy resin of a semiconductor-sealing-purpose, said composition comprises (A) Resins, epoxy, (B) resol, (C) curing catalyst and (D) has the microcapsule that contain curing catalyst of core/shell structure that wherein the curing catalyst as the nuclear core is packaged in the shell that contains thermoplastic resin.
2. according to the composition epoxy resin of claim 1, be 95/5-1/99 with weight ratio of mixture wherein as the microcapsule that contain curing catalyst of component (D) as the curing catalyst of component (C).
3. according to the composition epoxy resin of claim 1, wherein said thermoplastic resin is that compound (I) is 100/0-30/70 with the mol ratio of compound (II) by the polyureas of the triisocyanate compound of the triisocyanate compound of formula (I) representative and formula (II) representative:
4. according to the composition epoxy resin of claim 1, wherein the Resins, epoxy as component (A) is biphenyl type epoxy resin.
5. according to the composition epoxy resin of claim 1, wherein the resol as component (B) is phenol aralkyl resin.
6. according to the composition epoxy resin of claim 3, wherein said polyureas mainly comprises the repeating unit of formula (III) representative:
Wherein R represents divalent organic group; R 1And R 2Can be identical or different, respectively be hydrogen atom or any monovalent organic radical group.
7. one kind comprises the semiconducter device with the semiconductor element of each composition epoxy resin encapsulation among the above-mentioned claim 1-6.
CNB991251504A 1998-12-08 1999-09-30 Epoxy resin composition for packaging semiconductor and semiconductor device thereof Expired - Fee Related CN1238421C (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP34911298 1998-12-08
JP349112/98 1998-12-08
JP349112/1998 1998-12-08
JP11248523A JP2000230039A (en) 1998-12-08 1999-09-02 Semiconductor sealing epoxy resin composition and semiconductor device using same
JP248523/1999 1999-09-02
JP248523/99 1999-09-02

Publications (2)

Publication Number Publication Date
CN1256288A CN1256288A (en) 2000-06-14
CN1238421C true CN1238421C (en) 2006-01-25

Family

ID=26538820

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB991251504A Expired - Fee Related CN1238421C (en) 1998-12-08 1999-09-30 Epoxy resin composition for packaging semiconductor and semiconductor device thereof

Country Status (7)

Country Link
US (1) US6248454B1 (en)
EP (1) EP1009025A3 (en)
JP (1) JP2000230039A (en)
KR (1) KR100581988B1 (en)
CN (1) CN1238421C (en)
MY (1) MY116439A (en)
TW (1) TW500759B (en)

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6410615B1 (en) * 1998-06-09 2002-06-25 Nitto Denko Corporation Semiconductor sealing epoxy resin composition and semiconductor device using the same
US6342309B1 (en) * 1999-08-19 2002-01-29 Shin-Etsu Chemical Co., Ltd. Epoxy resin composition and semiconductor device
JP2001055431A (en) * 1999-08-19 2001-02-27 Shin Etsu Chem Co Ltd Epoxy resin composition for sealing semiconductor and semiconductor device
JP3995421B2 (en) * 2001-01-19 2007-10-24 株式会社ルネサステクノロジ Epoxy resin composition for semiconductor encapsulation and semiconductor device using the same
JP4742435B2 (en) * 2001-03-28 2011-08-10 住友ベークライト株式会社 Epoxy resin composition and semiconductor device
JP2004231932A (en) * 2002-12-02 2004-08-19 Nitto Denko Corp Adhesive composition, adhesive film, and semiconductor device using this
EP1420035B1 (en) * 2002-11-12 2007-06-06 Nitto Denko Corporation Filled epoxy resin composition for semiconductor encapsulation and semiconductor using same
JP4381255B2 (en) * 2003-09-08 2009-12-09 ソニーケミカル＆インフォメーションデバイス株式会社 Latent curing agent
JP4799883B2 (en) * 2005-03-01 2011-10-26 日東電工株式会社 Epoxy resin composition cured body, method for producing the same, and optical semiconductor device using the same
KR100830775B1 (en) * 2005-03-01 2008-05-20 닛토덴코 가부시키가이샤 Epoxy resin composition for photosemiconductor element encapsulation and photosemiconductor device using the same
JP5285841B2 (en) * 2005-04-12 2013-09-11 デクセリアルズ株式会社 Method for producing film adhesive
WO2006109831A1 (en) * 2005-04-12 2006-10-19 Sony Chemical & Information Device Corporation Processes for production of adhesives
JP4931366B2 (en) * 2005-04-27 2012-05-16 東レ・ダウコーニング株式会社 Curable silicone composition and electronic component
JP5285846B2 (en) * 2006-09-11 2013-09-11 東レ・ダウコーニング株式会社 Curable silicone composition and electronic component
JP5146645B2 (en) 2007-08-28 2013-02-20 デクセリアルズ株式会社 Microcapsule type latent curing agent
CN101249409B (en) * 2008-03-20 2010-06-02 江南大学 Preparation method of embedding amines active substance microcapsule and applications thereof
CN101851386B (en) * 2009-04-01 2012-09-05 汉高华威电子有限公司 Epoxy resin compound
CN101955629B (en) * 2009-07-16 2011-12-07 中芯国际集成电路制造(上海)有限公司 Epoxy resin composition capable of being used as semiconductor encapsulating material
US20130303639A1 (en) * 2010-12-28 2013-11-14 Hiroshi Yamauchi Resin composition for expansion molding
CN104603161B (en) * 2012-09-06 2016-11-09 积水化学工业株式会社 Curing agent and/or curing accelerator compound particle and their manufacture method and hot curing resin composition
KR101799499B1 (en) * 2014-12-24 2017-12-20 주식회사 엘지화학 Adhesive composition for semiconductor, adhesive film, dicing die bonding film, and semiconductor device
KR101927631B1 (en) * 2017-07-27 2018-12-10 주식회사 케이씨씨 Epoxy resin composition and semiconductor device comprising the same

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5681906A (en) * 1979-12-07 1981-07-04 Toshiba Corp Heat resisting electrical insulated coil
US5294835A (en) * 1992-07-28 1994-03-15 Nitto Denko Corporation Epoxy resin composition for semiconductor encapsulation and semiconductor device using the same
JP2716636B2 (en) * 1992-12-21 1998-02-18 住友ベークライト株式会社 Resin composition for semiconductor encapsulation
JPH08176280A (en) * 1994-12-27 1996-07-09 Matsushita Electric Works Ltd Liquid epoxy resin composition and its production
JP3340882B2 (en) * 1995-05-02 2002-11-05 日東電工株式会社 Epoxy resin composition for encapsulating semiconductor element and resin-encapsulated semiconductor device
JP3587640B2 (en) * 1996-12-13 2004-11-10 日東電工株式会社 Thermosetting resin composition and semiconductor device using the same
JPH10168164A (en) * 1996-12-13 1998-06-23 Nitto Denko Corp Epoxy resin composition and semiconductor device using the same
JPH10189832A (en) * 1996-12-20 1998-07-21 Nitto Denko Corp Epoxy resin composition and semiconductor device using the same
JPH10182943A (en) * 1996-12-20 1998-07-07 Nitto Denko Corp Epoxy resin composition and semiconductor device produced by using the composition

Also Published As

Publication number Publication date
MY116439A (en) 2004-01-31
EP1009025A2 (en) 2000-06-14
EP1009025A3 (en) 2002-08-28
US6248454B1 (en) 2001-06-19
KR20000047506A (en) 2000-07-25
TW500759B (en) 2002-09-01
JP2000230039A (en) 2000-08-22
CN1256288A (en) 2000-06-14
KR100581988B1 (en) 2006-05-23

Similar Documents

Publication Publication Date Title
CN1238421C (en) Epoxy resin composition for packaging semiconductor and semiconductor device thereof
CN1083851C (en) Epoxy resin composition
CN1262599C (en) Thermosetting resin composition and semiconductor device obtained therefrom
CN1077121C (en) Semiconductor encapsulating epoxy resin compositions and semiconductor devices encapsulated therewith
KR20050117547A (en) Resin composition for sealing semiconductor and semiconductor device using the same
JP7571814B2 (en) Epoxy resin composition and electronic component device
KR101254524B1 (en) Epoxy resin composition and semiconductor device
CN115785621A (en) Epoxy resin composition for sealing and electronic component device
CN101077967A (en) Epoxy resin composition for enveloping semiconductor and semiconductor device
JP6389382B2 (en) Semiconductor encapsulating resin sheet and resin encapsulating semiconductor device
CN112980138A (en) Epoxy resin composition for packaging electronic components and preparation method thereof
CN1113083C (en) Semiconductor sealing epoxy resin compsn. and semiconductor device using same
JPH04202524A (en) Epoxy resin composition and cured material thereof
WO2005097892A1 (en) Epoxy resin composition for the encapsulation of semiconductors and semiconductor devices
JP4958720B2 (en) Molded products and semiconductor packages
CN1676565A (en) Epoxy resin composition for semiconductor encapsulation and semiconductor device using the same
CN1330704C (en) Epoxy resin composition and method for producing epoxy resin composition and semiconductor device obtained thereby
CN1057402C (en) Method for packing semiconductor
KR20190096741A (en) Epoxy resin composition
CN100352847C (en) Resin composition for encapsulating semiconductor chip and semiconductor device therewith
KR101112043B1 (en) Epoxy resin composition for sealing semiconductor element
JP2837538B2 (en) Semiconductor device
JPH0582675A (en) Semiconductor device
JPH0647613B2 (en) Epoxy resin molding material for electronic parts encapsulation
JP2001335621A (en) Epoxy resin composition and semiconductor device

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20060125

Termination date: 20150930

EXPY Termination of patent right or utility model